Anthraquinone containing monoazo dyestuffs



United States Patent Olhce US. Cl. 260-2071 8 Claims ABSTRACT OF THEDISCLOSURE Difficultly water-soluble l-aminoand l-loweralkylamino-4-phenylamino-anthraquinone dyestuffs free from salt-forming,water-solubilizing groups which dissociate acid in water, bearing in morp-position at the benzene nucleus of the phenylamino substituent asubstituent of the formula N==NZ wherein Z represents an optionallysubstituted carbocyclic aromatic or heterocyclic aromatic radical and atthe same benzene nucleus optionally further substituents, while the2-position of the anthraquinone nucleus is occupied by an organicallyesterified or an amidified carboxyl group; these dyestuffs being suitedparticularly for the dyeing, from an aqueous dispersion, of hydrophobicorganic fiber materials, e.g. polyglycol terephthalate type fibers, butalso other polyester fibers and synthetic polyamide andpolyacrylonitrile fibers; processes of dyeing such hydrophobic organicfiber materials with such dyestuffs, and such fiber materials dyed withsuch dyestuffs.

wherein R represents hydrogen or a lower alkyl group,

X represents the radical of an organic hydroxyl compound bound by way ofan oxygen, or a primary, secondary or tertiary amino group, and

Y represents a mobile substituent enabling nucleophilic substitution,

with an amine of Formula II Z represents an optionally substitutedcarbocyclic-aromatic or heterocyclic-aromatic radical, and

Patented Nov. 17, 1970 the benzene ring A can have other substituents,preferably such that do not dissociate acid in water, to form a compoundof Formula HI wherein R and X have the meanings given for Formula I andZ and A have those given for Formula II. The starting compounds are tobe so chosen that the final dyestufi does not contain any salt-forming,Water-solubilising groups which dissociate acid in water such assulphonic acid, carboxylic acid or phosphonic acid groups.

As lower alkyl group, R represents, e.g. isopropyl, ethyl and,especially, methyl; preferably however, R is hydrogen.

As radical of an organic hydroxyl compound bound by way of oxygen, Xrepresents, for instance, the group OR wherein R is an optionallysubstituted aliphatic, cycloaliphatic, carbocyclic aromatic orheterocyclicaromatic radical.

When X is a primary, secondary or tertiary amino (III) group, then itis, particularly, a group of the formula wherein R is hydrogen or thesame as R R, is hydrogen or an optionally substituted aliphatic orcycloaliphatic radical, or R and R together with the nitrogen atom towhich they are linked represent, optionally with the inclusion ofanother hetero atom, a 5- or 6-membered heterocyclic ring.

Accordingly, the dyestuffs according to the invention constitute twosubclasses, one in which the 2-position of the anthraquinone nucleus issubstituted by an esterified carboxyl group of the formula -cooR,

and another subclass in which the aforesaid 2-position is occupied by anamidified carboxyl group of the formula R R and R having the meaningsgiven above.

The dyestuffs of the first-mentioned subclass afford dyeings onhydrophobic fibers which are generally of greater light-fastness thanthose obtained with dyestuffs of the second subclass.

In each of these subclasses, the dyetulfs in which Z represents anoptionally substituted monoor dinuclear.

When R R and R represent aliphatic radicals these are, e.g. straight orbranched chain, optionally substituted alkyl or alkenyl groups, and inthe latter case, particularly A -alkenyl groups, having preferably up tocarbon atoms. As substituents, these aliphatic radicals can contain,e.g. hydroxyl or preferably alkoxy groups, such as unsubstituted alkoxy,alkoxyalkoxy or alkoxyalkoxyalkoxy groups, or alkoxycarbonyl groups,wherein the alkoxy moiety has from 1 to 3 carbon atoms. As substitutes,they can also contain carbocyclic rings, especially of aromaticcharacter, such as the phenyl radical, or heterocyclic rings, such asthe thienyl- (2), furyl-(2) or tetrahydrofuryl-(2) radical.

Cycloaliphatic radicals symbolised by R R and R are, e.g. cycloalkylgroups with, preferably, 5- or 6- membered rings and, especially, thecyclohexyl or methylcyclohexyl group.

As carbocyclic-aromatic radicals represented by R and R mononuclearsubstituents of the benzene series are preferred, especially anunsubstituted phenyl group or a phenyl group substituted by at least oneand preferably not more than three of the following substituents: nitro,chlorine, bromine, fluorine, alkyl, alkoxy, and/or one of thesubstituents hydroxy-alkyl, alkoxy-carbonyl, alkyl-sulfonyl oralkyl-sulfonyloxy, alkyl and alkoxy portions having at most 4 carbonatoms.

If R and R represent heterocyclic-aromatic radicals, then these arepreferably 5- to 6-membered cyclic radicals, especiallynitrogen-containing rings of aromatic character, e.g. pyridine radicals,more partcularly the pyridyl- (3) radical.

When R, and R together with the nitrogen atom to which they are linkedrepresent a 5- or 6-membered heterocyclic ring, then this is, e.g., thepyrrolidino, piperidino, piperazino, thiomorpholino or, especially, themorpholino ring.

Dyestuffs falling under Formula III in which R represents an alkylradical having at most 3 carbon atoms or such an alkyl radicalsubstituted 'by alkoxy, alkoxyalkoxy or alkoxyalkoxyal'koxy groupshaving from 1 to 3 carbon atoms per alkoxy portion, or in which each ofR and R represent an alkyl group having at most 3 carbon atoms, haveparticularly good drawing power onto organic hydrophobic fibres and goodfastness to sublimation and to light.

When Z is a carbocyclic-aromatic radical, then it it, e.g. a naphthyl orpreferably a mononuclear residue of the benzene series.

When Z is a heterocyclic-aromatic radical, then it is for example anazolyl radical which can be condensed, I

particularly with a benzene nucleus. Examples are 2- loweralkyl-indoyly-(3) radicals, the diazolyl radicals such as pyrazolylradicals, e.g. l-lower alkyl-pyrazolyl- (5) or 1-phenyl-3-loweralkyl-S-hydroxypyrazolyl-(4) radicals, l-lower alkyl-indazolyl-(3)radicals or imidazolyl radicals, e.g. benzimidazolyl-(Z) radicals, orthe thiazolyl radicals such as thiazolyl-(2) or benzothiazolyl-(2)radicals. Also azinyl groups, e.g. pyridyl groups such as thepyridyl-(3) group can be in the position of Z.

The carbocyclic-aromatic rings in X and Z as well as the benzene ring Acan contain other substituents which do not dissociate acid in water,rendering the dyestuffs water-soluble, and do not elongate the resonancesystem, hence not detrimentally affecting the purity of the shade of thedyestuffs; suitable substituents are especially halogen, e.g. fluorine,chlorine or bromine, nitro, lower alkyl, hydroxy-lower alkyl, loweralkoxy, but also lower alkoxy-carbonyl, lower alkyl-sulfonyl or loweralkylsulfonyloxy groups.

In the specification, including the claims, the term lower applied toalkyl and alkoxy means such groups having 1 to 5 carbon atoms.

In preferred dyestuffs falling under Formula III, which are dstinguished by good drawing power and fastness to sublimation and light,Z represents an unsubstituted phenyl or naphthyl radical, or a naphthylor, especially, a phenyl group substituted by at least one andpreferably not more than three of the following substituents: nitro,chlorine, bromine, fluorine, alkyl, alkoxy, and/or one of thesubstituents hydroxy-alkyl, alkoxy-carbonyl, alkyl-sulfonyl oralkyl-sulfonyloxy, alkyl and alkoxy portions having at most 4 carbonatoms; ring A in these preferred dyestuffs is either without additionalsubstituents apart from the grouping -N=NZ, or substituted by methyl,methoxy and/or chlorine.

Most preferred are those of the above class of dyestuffs falling underFormula III in which Z represents a phenylor methyl-substituted phenylgroup and in which R or, as the case may be, R and K; have theabove-mentioned preferred significance.

In these most preferred dyestuffs, the ring A is either without furthersubstitution or bears one or several, preferably not more than three,methyl groups.

In the starting compounds of Formula I, Y, as mobile substituentenabling nucleophilic substitution, represents e.g. halogen such aschlorine or bromine, a lower alkoxy group such as the methoxy or ethoxygroup, the hydroxyl or the nitro group. Preferably, however, Y isbromine, or also chlorine.

Some of the starting materials of Formula I are known or can be producedby methods known per se, e.g. by converting ananthraquinone-2-carboxylic acid of the formula 0 PIMP-R1 COOII into itscarboxylic acid chloride or bromide and reacting the latter with anorganic hydroxyl compound, ammonia or a primary or secondary amine.

Examples of starting materials of Formula I are:

1-amino-2-carbalkoxy-, 1-amino-2-carbo-(hydroxyalkoxy)-,1-amino-2-alkoxycarbalkoxy-, l-amino-2-carbo-(phenylalkoxy)-,l-amino-2-carbofurfuryloxyor1-amino-2-carbo-tetrahydrofurfuryloXy-4-chloroor-4-bromo-anthraquinones, l-amino-2-carbocyclo-alkoxy-4-chloroor-4-bromo-anthraquinones, 1-amino-2-carbophenoxy-4-chloroor-4-bromo-anthraquinone, 1-arnino-2-carbo-(pyridyloxy)-4-chloroor-4-bromo-anthraquinone,

1-amino-4-chloroor -4-bromo-anthraquinone-2-carboxylic acid amide,

-2-carboxylic acid-N-alkylamides,

as well as the corresponding l-methylamino analogues.

The greater part of the aminoazo compounds of Formula II-which can beused as starting materials are also known or they can be produced by theusual methods by coupling diazotised nitroanilines or acylamino anilineswith coupling components and subsequent reduction of the nitro group orhydrolysis of the acylamino group to the amino group.

The condensation of starting materials of Formula I with the amines ofFormula II is performed, e.g. with an excess of amine in a melt at70-250 C. It is preferably performed, however, in an inert organicsolvent at reaction temperatures of 100-160 C. in the presence of anacid binding agent and a catalyst.

Aromatic hydrocarbons such as toluene or xylenes, halogenated aromatichydrocarbons such as chlorobenzene or dichlorobenzenes, or nitratedaromatic hydrocarbons such as nitrobenzene can be used, for example, asinert organic solvents. Alcohols are particularly suitable, especiallyalkanols having at least two carbon atoms, e.g. ethanol, noriso-propanol, butanols or amyl alcohols, or alkylene glycols and theirmonoalkyl ethers, e.g. ethylene glycol and its monomethyl or monoethylether.

Alkali metal hydroxides, particularly sodium or potassium hydroxides,alkali metal carbonates, especially sodium or potassium carbonate andalkali metal salts of lower fatty acids such as alkali metal acetatesare mentioned as preferred acid binding agents.

Copper or copper-(I) salts such as copper-(I) acetate or chloride arementioned as preferred catalysts.

A modification of the process according to the invention for theproduction of new, difficultly water-soluble anthraquinone dyestufis ofFormula III consists in condensing an anthraquinone compound of FormulaIV C O-Hal wherein Hal represents chlorine or bromine and R has themeaning given for Formula I, and Z and A have those given for FormulaII, with a compound of Formula V H-X (V) wherein X has the meaning givenfor Formula I, to form a compound of Formula III, the components beingso chosen thatthe final dyestulf contains no salt-forming,Water-solubilising groups which dissocate acid in water.

The anthraquinone compound of Formula IV is obtained, e.g be reactingthe corresponding anthraquinone-2- carboxylic acid with a halogenatingagent such as thionyl chloride or phosphorus pentachloride by usualmethods. The condensation of the anthraquinone compound of Formula IVwith the compound of Formula V is performed in a known way,advantageously in an inert organic solvent, e.g. in an aromatichydrocarbon, halogenated or nitrated hydrocarbon or in water and,optionally, in the presence of 'acidbinding agents.

A second modification of the process according to the invention for theproduction of compounds of Formula III wherein R is hydrogen consists inreducing an anthraquinone compoud of Formula VI 1 wherein X has themeaning given for Formula I, and Z and A have those given for FormulaII, the components being so chosen that the end product obtained doesnot contain any salt-forming, water-solubilising groups which dissociateacid in water.

The reduction is advantageously performed with watersoluble sulphides orhydrogen sulphides in aqueous dispersion or in aqueous-organic solutionor dispersion. The organic part of such mixtures preferably consists ofwatermiscible, inert, organic solvents such as tertiary nitrogen bases,e.g. pyridine or homologues thereof, or it consists of amides of lowfatty acids such as N,N-dimethyl formamide, or of aliphatic alcoholse.g. alkylene glycol monoalkyl ethers, for example ethylene glycolmonomethyl or monoethyl ether.

A third modification of the process according to the invention for theproduction of new, difiicultly water-soluble anthraquinone dyestuffs ofFormula III consists in condensing an anthraquinone compound of FormulaVII wherein X and Y have the meanings for Formula I, and Z and A havethose given for Formula II, with an amine of Formula VIII wherein R hasthe meaning given for Formula I, the starting compounds being so chosenthat the end product obtained does not contain any salt-forming,water-solubilising groups which dissociate acid in water.

Starting materials of Formula VII are obtained, for example, bycondensing equivalent amounts of an anthraquinone compound of theformula I O Y I I with an aminoazo compound ofthe formula wherein A, X,Y and Z have the meanings given above.

A further modification of the process according to the invention for theproduction of anthraquinone dyestuifs of Formula III wherein Xrepresents a primary, secondary or tertiary amino group, consists incondensing an anthraquinone compound of Formula IX wherein X representsthe radical of an organic hyd roxyl compound bound by way of oxygen,

Q represents a nitro or an amino group NHR R being hydrogen or a loweralkyl group, and

Z and A have the meanings given for Formula II,

with ammonia or a primary or secondary amine and, if Q is a nitro group,reducing said nitro group simultaneously to the amino group NH thestarting compounds being so chosen that the end product obtained doesnot contain any salt-forming, water-solubilising groups which dissociateacid in water.

The conversion of the esters of Formula IX into the corresponding amidesand optional reduction of the nitro group are carried out, preferably inan excess of ammonia or amines, and, optionally, in the presence ofinert organic solvents such as given above for the other processes.

When producing the new anthraquinone dyestuffs of Formula III, theygenerally precipitate from the reaction mixture or they can beprecipitated from the reaction mixture by the addition of water or ofwater-miscible, inert organic solvents, e.g. lower alkanols. In the purestate, they are shimmering deeply coloured, crystalline substances.

Advantageously, the dyestuffs according to the invention are broughtinto a finely distributed form by milling with dispersing agents. Forthis purpose, anionic dispersing agents, e.g. alkylaryl sulphonates,condensation products of formaldehyde and naphthalene sulphonic acids,lignin sulphonates, or non-ionogenic dispersing agents such as fattyalcohol or higher alkylphenyl polyglycol ethers are suitable. Thedyestuffs according to the invention are preferably milled with suchdispersing agents with the addition of water. The resultant, aqueousdyestuff pastes which contain the dyestuffs in finely distributed formcan either be used direct for dyeing or they can be formulated intonon-dusty powders by careful drying according to known methods.

In such preparations, the dyestuffs according to the invention aresuitable for the dyeing of organic material, particularly of hydrophobicorganic fibre material, from an aqueous dispersion, e.g. for the dyeingof cellulose ester fibres such as cellulose di-, 2/;:- or tri-acetate,preferably however, they are suitable for the dyeing of textile fibresmade from polyesters of aromatic polycarboxylic acids with polyvalentalcohols such as polyglycol terephthalate, polyglycol isophthalate orpolycyclohexane diol terephthalate fibres.

The dyestuffs can also be used, however, for the dyeing of syntheticpolyamide fibres such as polyamide 6, 66 or 11.

In some cases, also valuable dyeings can be attained with the dyestuffsaccording to the invention on polyacrylonitrile fibres.

Polyglycol terephthalate fibres are dyed with aqueous dispersions ofdyestuffs according to the invention, for example, at temperatures ofover 100 C. under pressure. Dyeing can also be peformed, however, at theboiling point of the dye liquor in the presence of carriers, e.g. alkaliphenyl phenolates such as sodium-o-phenyl phenolate, polychlorobenzenecompounds or similar auxiliaries. Very good dyeings are also obtained ifthese fibres are impregnated with concentrated aqeuous dispersions ofdyestuffs according to the invention, then squeezed out, dried and thedyestuffs are finally fixed at temperatures of 100-250 C. In many cases,the drawing power of the dyestuffs onto these fibres and the stabilityof the aqueous dispersions in the dye liquor can be improved by mixingtwo or more dyestuffs of similar composition of which at least one isembraced by Formula III.

Compared with corresponding dyeings attained wih known green dyestuffsof similar constitution under the same conditions, the green dyeingsattained with the dyestuffs according to the invention on hydrophobicpolyester fibre material, particularly polyglycol terephthalate fibres,have a substantially greater colour strength and/ or fastness tosublimation and to light. The colour strength may be improved as much as50 to Moreover, vegetable and animal fibres, particularly cotton, arewell reserved by the dyestuffs according to the invention. Anotheradvantage of the dyestuffs according to the invention is that they aresuitable for use in the so-called thermosol dyeing process, for whichhigh grade fastness to sublimation is a prerequisite. When used in thisway, they also provide level, green dyeings which are fast to rubbing.

Practically all polymeric hydrophobic materials can be dope-dyed withthe dyestuffs according to the invention. Hydrophobic organic fibres andespecially the above mentioned synthetic polyester fibres, e.g. thefibres consistin of linear high molecular ester of aromaticpolycarboxylic acid with polyfunctional alcohol can be dyed from anaqueous dispersion of the dyestuffs according to the invention. 7

Colouration of the organic materials is effected in either case bypenetration of dyestuff molecules into the organic material, especiallythe fibres, and partial reagglomeration to larger dyestuff particles inthe interior of the fibres.

The following non-limitative examples illustrate the invention further.The temperatures are given therein in degrees centigrade. Percentagesare given by Weight.

EXAMPLE 1 C O 0 CH3 36 g. of l amino2-carbomethoxy-4-bromoanthroquinone, 59 g. of 4-aminoazobenzene, 22.1 g.of anhydrous potassium acetate and 1 g. of copper-(I) chloride are addedto 100 g. of amyl alcohol, the reaction mixture is stirred untilhomogeneity is attained and kept for 10 hours at -135 The reactionmixture, which has become yellow-green coloured, is then cooled to 90",200 g. of ethanol are added and then it is stirred for another 3-4 hoursat room temperature. The dyestuff of the above formula precipitates as adark grey-green crystalline powder. This is separated by filtration,washed, dried and recrystallized to further purify from ethylene glycolmonomethyl ether.

From aqueous dispersion, the new dyestuff dyes polyethylene glycolterephthalate fibre material in clear green shades which have very goodfastness to light and sublimation.

If, instead of the 36 g. of l-amino-carbomethoxy-4- bromoanthraquinone,equimolar amounts of one of the anthraquinone compounds given in thefollowing table, columns I and II, are used and if, instead of the 59 g.

. of 4-aminoazobenzene, equimolar amounts of one of the aminoazocompounds given in column III of the same table are used, then withotherwise the same procedure as given in the example, dyestuffs areobtained which dye polyglycol terephthalate fibre material in the shadesgiven in column IV of this table. The dyeings are also fast to light andsublimation.

TABLE-Continued Anthraquinone compound fl) NH-R1 Shade of dyeing 0 Br onpolyglycol terephthalate No. -NH-R1 -O0-X Ammoazo compound fibres 26-NH1 I I ....do Green.

27 NHa -o o 0 011mm), n Do.

CH; 28 --Nm --0 o 0 0 do Do,

29 -Nm --0 o o 0 (0mm .-.-do Do;

0:115 30 -Nm -0 o 0 0 (CH3): NED-N: Do.

32 N 0 2-0 =c112 NHrN=N m as --NH: 41000211 NHr-N=NNm Do.

34 -NHa 40002115 NHz-@N= Q Do.

I CH3 35. --NH1 --0 o o omomo CH: NHz-Q-N: Do;

36 -NH: --0 0(0 cmcnmo 01H; NHQN= Do;

37 --NH1 -0 o o cmomomo CH3 NHQN=N--Br Do.

as -NH2 42000113 NHrN=N F Do.

/CH3 a9 -NH: -co0cH NHz-N=N- Do;

CHzO CH3 /CH| 4o -NHI -0000H NHQN=N Do;

0 O 0 0211 41 --NH2 42000211, NHr-N=N- SOzCH: Do.

42 --NH2 -0o00H3 NH-N=N Do.

5* 43 NHz oo 0 02m NHr-N=NEQO s 01cm m.

CE: W 44 -NH0H, -c ONHCH; NHQN: Do.

011 GH2CH2OH N 45... NH2 --0 ON NH. N=N- Do.

GH CH OH TABLE-Continued Anthraquinone compound lfH-Rl Y I Shade ofd einBr 0n polygly eol g terephthalate N0. -NHR1 -C OX Ammoazo compoundfibres 64 NHz CHa Green.

. NH N=N -C OO l 65 NH2 N02 Do.

66 --NHCH3 Do.

--GOO -01 NHz- N=N CH2CH2OH 67 NH2 D0.

-CO-O NET -N=N CH2CH2OH 68 NH2 C1 Do.

oo o tm NHr@ N=N CH2CH20H o9 NH2 0 Do.

-o o-oQm NH2-N=N-CH2CH2OH 70 -NH2 F Do; -oo-o NHz-N=NCHCHOH 71 NH2 Do:

COO CHzCHaOH NH N=N(}-fi}-QH 72 NH Do;

2 -CO-OCOOCH3 NHrN=N- a 2 o 0-0 (32115 NH2-N=N Do;

N 73 -NH2 S 202 Do;

4 NH Do.

EXAMPLE 75 0 M12 102 g. of 4-(1'-phenyl-3'-methyl-5'-hydroXy)-parazolyl-(4-azo)-1-aminobenzene, 37.3 g. of 1-amino-4-brornoanthraquinone-Z-carboxylic acid-N,N-dimethylamide, 25 g. of anhydrouspotassium acetate and 1 g. of copper-(I) acetate in 200 g. of ethyleneglycol monethyl ether are stirred for 15 hours at -135 and then g. ofmethanol are added at 80. The reaction product of the above formulaprecipitates in a finely crystalline form. It is separated byfiltration, washed, dried and recrystallised from pyridine.

After developing at about 200 on polyglycol terephthalate fabric whichhas been impregnated with the aqueous dispersion of this dyestuff andthen dried, a deep green dyeing having excellent fastness to light andsublimation is obtained.

EXAMPLE 76 CONH2 34.5 g. of 1-amino-4-bromoanthraquinone-Z-carboxylicacid amide, 90 g. of 4-amino-4'-methoxyazobenzene, 10 g. of sodiumbicarbonate and 1.6 g. of copper-(I) acetate in 150 g. of isoamylalcohol are stirred for 8 hours at 120-130". 100 g. of ethanol are thenadded to the reaction mixture; it is cooled to room temperaturewhereupon the condensation product of the above formula precipitates. Itis separated by filtration, washed and dried.

The new dyestulf draws from aqueous dispersion onto polyglycolterephthalate or cellulose triacetate fabric in clear green shades whichhave very good fastness to sublimation.

EXAMPLE 77 fl) NHQ COOGH:

' 3 3 NH- N=N CH: CH;

31.6 g. of 1-amino-2-carbomethoxy-4-chloroanthraquinone, 67.5 g. of4-amino-3,2-dimethyl-azobenzene, 22.1 g. of anhydrous potassium acetateand 1 g. of copper-(I) chloride in 120 g. of n-butanol are stirred for24 hours at 115120, the reaction mixture is cooled to room temperatureand 180 g. of methanol are added. The dyestuff of the above formulaprecipitates from the solution in finely crystalline form. It isseparated by filtration, washed and dried.

The dyestutf obtained is mixed in a weight ratio of 1:1 with thedyestutf obtained according to Example 1. The mixture is milled withsand to attain a fine distribution and disparsed in a condensationproduct of naphthalene sulphonic acids and formaldehyde. From thisdispersion the dyestutf mixture draws onto polyglycol terephthalatefibre material in vivid green shades which are fast to wet, light and,particularly, sublimation.

EXAMPLE 78 O IIIHCH:

COOCH$ 4'-chloroazobenzene are stirred for 5 hours at 3540 in 200 g. ofa 35% aqueous solution of methylaminc. The reaction mixture is cooled to1015, the reaction product formed of the above formula is separated byfiltration, washed with water until the reaction is neutral and dried.The dyestutf obtained dyes polyglycol terephthalate fabric from anaqueous dispersion by the thermosol process in clear green shades whichhave excellent fastness to wet, sublimation and light.

EXAMPLE 79 52 g. of1-nitro-2-carbethoxy-4-(4'-phenylazo-phenylamino)-anthraquinone areslurried in 500 ml. of ethanol. A stream of ammonia is introduced forhalf an hour into this dispersion until saturation is attained whereuponthe dispersion is heated to 60-70 in a steel autoclave while stirring orshaking. At 15 minute intervals, the ammonia used up by the reaction isreplaced by application of ammonia from a steel cylinder in such amanner that the pressure in the reaction vessel remains constant. Thereaction mixture is then kept for another hour at this temperature andcooled to room temperature, whereupon the obtained residue is filteredoflf, washed with water until the reaction is neutral and then dried.

The dyestutf is a dark grey-blue crystalline powder. It dyes polyglycolterephthalate fibres from an aqueous dispersion in clear green shadeswhich have excellent light and sublimation fastness.

The same dyestufi" is obtained if instead of 52 g. of 1- nitro 2carbethoxy 4-(4-phenylazo-phenylamino)- anthraquinone, 49.2 g. of 1amino-2-carbethoxy-4-(4- phenylazo-phenylamino)-anthraquinone or 49.3 g.of 1- nitro 2 carbamyl 4-(4-phenylazo-phenylamino)-an thraquinone areused as starting materials and otherwise the condensation is carried outas described above.

EXAMPLE 80 16 g. of 70% sodium hydrogen sulphide are added at -90 to thepartial solution of 52 g. ofl-nitro-Z-carbethoxy-4-(4-phenylazo-phenylamino)-anthraquinone in 300 g.of 50% aqueous pyridine and the reaction mixture is then stirred for 10minutes at this temperature. The

21 blue-green dispersion formed is diluted with 300 ml. of water, cooledto room temperature and the reaction product is separated by filtration,washed and dried. The dyestuff obtained dyes polyglycol terephthalatefibres from an aqueous dispersion in clear green shades which haveexcellent light and sublimation fastness.

34.6 g. of 1-amino-4-bromoanthraquinone-2-carboxylic acid, 59.1 g. of3-aminoazobenzene, 22.1 g. of anhydrous potassium acetate and 0.8 g. ofcopper powder are stirred in 115 g. of n-amyl alcohol for 20 hours at1l5l20. 60 g. of methanol are then added to the reaction mixture whichis then cooled to room temperature whereupon the condensation productprecipitates. This is dissolved in 5% sodium bicarbonate solution,filtered to clarify, the filtrate is acidified with hydrochloric acidand the precipitated product is separated by filtration, washed anddried.

37.0 g. of the condensation product so obtained are boiled in 250 g. ofthionyl chloride for 5 hours. The excess thionyl chloride is thenremoved in vacuo, the residue is taken up in 200 g. of o-dichlorobenzeneand, after the addition of 67 g. of anhydrous methanol, the whole isstirred for 6 hours at 80-90". The reaction mixture is then cooled to 0-l0 whereupon the reaction prodnet of the above formula crystallises outin a very pure form. It is filtered 0E, washed and dried. Polyglycolterephthalate fabric is dyed from an aqueous dispersion of the dyestufi.so obtained in pure green shades which have excellent sublimation andwet fastness properties.

EXAMPLE 82 2 g. of the mixture of dyestuffs described in Example 4- aredispersed in 4000 ml. of water which contains 12 g. of sodium-o-phenylphenolate and 12 g. of diammonium phosphate, and 100 g. of a polyglycolterephthalate fabric are introduced into the dyebath. Dyeing isperformed for 1 /2 hours at 95-98. The fabric is then rinsed andthoroughly washed with dilute sodium hydroxide solution and acondensation product of naphthalene sulphonic acids and formaldehyde. Agreen dyeing which is fast to sublimation, light and wet is obtained.

EXAMPLE 83 2 g. of the finely milled dyestuif obtained according toExample 1 are dispersed in 4000 ml. of water which contains 2 g. of acondensation product of naphthalene sulphonic acids and formaldehyde.The pH of the dyebath is adjusted to 6.5 with acetic acid. 100 g. ofpolyglycol terephthalate fabric are introduced into the dyebath at 40,the bath is heated within 15 minutes to 120 in a closed vessel and iskept for 45 minutes at this temperature. The fabric is then rinsed withwater and subsequently soaped. In this way a clear, green dyeing isobtained which has excellent fastness to sublimation, wet and light.

22 EXAMPLE s4 Polyglycol terephthalate fabric is impregnated in afoulard at 40 with a liquor of the followign composition:

G. Dyestuff according to Example 80, finely dispersed in 30 Sodiumalginate 7.5 Condensation product of formaldehyde and naphthalenesulphonic acids 10 and Water 950 The fabric which has been squeezed outto a liquor content of about (calculated on the dry weight of thefabric) is dried at 100 and then fixed for 60 seconds at a temperatureof 210. The dyed goods are rinsed with water, soaped and dried. Underthese conditions a green dyeing is obtained which is fast to washing,light and sublimation.

We claim:

1. A dyestuff free from salt-forming, water-solubilizing groups whichdissociate acid in water, which dyestutf is of the formula COOR2 whereinR represents hydrogen or a lower alkyl group, R represents (a)unsubstituted lower alkyl,

(-b) lower alkyl substituted by hydroxy, alkoxy, alkoxyalkoxy,alkoxyalkoxyalkoxy or alkoxycarbonyl, each of the preceding alkoxyportions having portions from 1 to 3 carbon atoms, or phenyl,

(c) alkenyl of at most 4 carbon atoms,

(d) cyclohexyl,

(e) methyl-cyclohexyl,

(f) phenyl, or

(g) phenyl monosubstituted by nitro, chlorine, bromine, fluorine, loweralkyl, lower alkoxy, hydroxy-lower alkyl, lower alkoxy-carbonyl, loweralkyl-sulfonyl or lower alkyl-sulfonyloxy;

Z represents (b) naphthyl, or

(c) phenyl monosubstituted by chlorine, bromine, fluorine, nitro, loweralkyl, lower alkoxy, hydroxy lower alkyl, lower alkoxy-carbonyl, loweralkylsulfonyl or lower alkylsulfonyl-oxy, and

ring A bears no further substituents or is further monosubstituted bymethyl, methoxy or chlorine.

2. A dyestuff as defined in claim 1 wherein R repesents unsubstitutedalkyl of at most 3 carbon atoms or such alkyl radical substituted by oneof the following:

alkoxy, alkoxyalkoxy, alkoxyalkoxyalkoxy or alkoxycarbonal each havingfrom 1 to 3 carbon atoms per alkoxy portion, and Z represents (a)phenyl, (b)

naphthyl, or (c) phenyl monosubstituted by chlorine,

bromine, fluorine, lower alkyl, lower alkoxy, nitro, hydroxyl-loweralkyl, lower alkoxyl-carbonyl, lower alkyl-sulfonyl or loweralkyl-sulfonyl-oxy.

3. A dyestuif as defined in claim 1 wherein R represents unsubstitutedalkyl of at most 3 carbon atoms or such alkyl radical substituted by oneof the following:

alkoxy, alkoxyalkoxy or alkoxyalkoxyalkoxy, each alkoxy portion havingat most 3 carbon atoms, Z

represents phenyl or methyl-phenyl, and ring A is without furthersubstituents or it is further substituted by one methyl group.

4. A dyestulf as defined in claim 2 which is of the 7. A dyestuff asdefined in claim 2 which is of the formula formula 8. A dyestuff asdefined in claim 2 which is of the 5. A dyestuff as defined in claim 2which is of the f l formula 0 NH; II I (EH3 0 111m Cm A COOCHCHz0CHz-c0oc l Y Q Q 0 NH- N:N u 1 O NH-N=N References Cited UNITED STATESPATENTS 6. A dyestuff as defined in claim 2 which is of the 2 145 954 21939 semple 2 0 19 X formula 2,598,587 5/1952 Moergeli 260207.12,920,072. 1/1960 Koelliker et al. 260207 o N112 l CHARLES B. PARKER,Primary Examiner -COO(CH ClIzO)z-CHa C. F. WARREN, Assistant ExaminerUS. Cl. X.R.

